Plastic mass



Patented July 25, 1933 unites stares PATENT ewes cuR'r scnoneuae, or BITTERFELD, GERMANY, ASSIGNOR To I. a; rAaBnnnvnusrmE AKTIENGESELLSCHAFT, OF FRANKFORT-ON-THE-MAIN, GERMANY 1 PLASTIC MASS No Drawing. Original application filed April 8, 1830, Serial No. 442,689, and. in Germany April 8, 1929.

Divided and this application filed July 9, 1931. Serial No. 549,809.

The present invention relates to a new compositionof matter in which new phosphoric acid esters of glycol monoethers are mixed or colloidized with'cellulose derivatives. The present application is a division of my copending application Ser. No. 442,689 concerning a method for producing the phosphoric acid esters of glycol ethers in question and their halogen derivatives.

The incorporation of this new group of phosphoric acid esters in plastic masses of cellulose derivatives results in an improvement of various qualities of the latter, particularly inasmuch as they are rendered non-sensitive to the efiects of low temperatures in a very high degree.

The tertiary phosphates of the uniform or mixed monoalkyl- (or aryl-) glycol-others are'colorless substances having a high boiling point, which are diiiiculty inflammable and exceedingly stable.

The particular advantages of the phosphoric acid esters described, as distinguished from the known esters of glycol-ethers of organic acids, substantially reside in their higher boiling point and their smaller vapor tension. The lower homologues of the uniform esters, as, for instance, tri (ethoxyethyl) phosphate of the formula (C3H5OO2H4) 1 04, are water soluble, whereas the higher homologues are not; substitution of only a single ethoxyethyl group by the butoxyethyl group may already suffice to produce insolubility in water.

The principalpoint of importance with respect to these various homologues consists in that they are particularly suitable as gelatinizers and softeners for nitroand acetylc'ellulose as well as for the most various cellulose esters and cellulose ethers; when employed in this manner the lower homologues display a greater dissolving capacity for the cellulose derivatives than the higher ones.

The dissolving efiiciency of these products towards cellulose derivatives which is repre sented by their different gelatinizing effect upon the latter, may be regulated and utilized. by correspondingly selecting the esterifying groups. Thus acetyl-cellulose is difiiculty gelatinized by of the formula:

(onnocgmo)3 1==0,

tri (butoxyethyl) phosphate whereas di (methox-yethyl) butoxyethyl phos- 6 easily effects gelatinization. The number of technically useful gelatinizers for cellulose derivatives is thus materially increased.

The effect of the new compounds upon the plastic masses produced from cellulose derviatives is remarkablein many respects; in all Cases inflammabilityof the masses is largely reduced. Further the addition of these substances to acetyl-cellulose increases the strength of the plastic masses, this increase beingv apparent from the raised pleating coeflicient as well as the improvement of the.

masses which were hitherto produced from acetyl-cellulose by means of known gelatinizers, as the brittleness of those massesis regularly strongly increased when'the latter are 1 subjected to low temperatures. Finally, also the fastness to light of the masses rendered plasticby means of the new esters is superior tothatlof masses hitherto knownl In further pursuance of the invention 1 have found that phosphoric acid esters of such glycolmonoethers which contain a halogen, for instance chlorine or bromine, have the same external appearance as the products made from non-substituted. glycolethers and are also capable of acting as gelati nizers and softeners. Moreover, they cause a further reduction of inflammability in the plastic masses madefrom acetyl-cellulose. vThey are advantageously employed in com 1 bination Withfthe nonhalogenized esters, as masses displaying a remarkable'clarity resulttherefrom.

The new gelatinizers and sotten ersabove described are employed in the art of producing plastic masses in exactly the same manner 7 in which such agents are generally applied in formula the celluloid or acetyl-cellulose art. They may also be used either by themselves or in combination with known softeners such as triacetin, phthalic acid ester etc. The proportion to be added is, also with respect to the new, substances, substantially governed by the qualities to be attained in the final'products.

The new phosphoric acid esters may further be advantageously substituted for the known softeners in the production of nitroor cellon lacquers as they leave a colorless clear coating after the organic solvents have evaporated; the coating, besides the known good qualities, has the further advantage of being highly fast to light and resistant to cold.

The following examples serve to illustrate my invention without limiting it to the specific details given therein.

E wample 1 high resistance to the influence of mechani-' cal stresses such asoccur in operationsinvolving a pleating, distending or'bending of the products. A further advantage of the new films resides in that their brittleness at zero temperature and below does not increase in the same degree as is the case with the films hitherto known.

Example 2 7 5 parts of acetyl-cellulose, 10 parts of di- (methoxyethyl) butoxyethylphosphate, 15 parts of tri(chloroethyl)phosphate of the are worked into cellon films in the manner known per se with the usual solvents. The product is a remarkably clear cellon film showing no opalescence Whatever, and a strongly reduced inflammability.

E wample 3 y Instead of the acetyl-cellulose compositions employed in the preceding examples the following composition proves equally suitable:

7 5 parts of acetyl-cellulose, 20 parts of monochloroethyl methoxyethyl butoxyethyl phosphate of the formula:

C1.CH2-OHz-O OH;0.0Hi-CHz.O-P=O O4H9O.CHCH2.O

' 5 parts of di(methoxyethyl)butoxyethylphosphate. v

As mentioned above, my invention is not limited to the foregoing examples and valuable plastic masses are likewiseobtainable when using the other neutral phosphates of glycolmonoethers described in my copending specification Serial No. 442,689. These glycol others from which I enumerate, for instance, tri (ethoxyethyl) phosphate, tri (phenoxyethyl) phosphate, tri (butoxypropyl) phosphate,

di (ethoxyethyl) butylphosphate, di (chloroethyl) ethoxyethylphosphate, and chloroethyl methoxyethyl butyl phosphate, are equivalents of those applicable according to the foregoing examples.

These compounds may be represented by the general formula:

o=ro o,rno ,.n"

waHi hR" wherein R is alkyl, halogenoalkyl or phenyl and m and 1 stand for 0 or 1. In this formula the ethylene radicle C I-L may be substituted A by, for instance, propylene. These homo-' logues are intended to be in the scope of the claims following hereafter.

I claim:

1.'A composition of matter comprising a cellulose derivative and a neutral phosphoric acid ester of a monoglycol ether of the gen eral formula.

Where R, R and R" represent alkyl halogenoalkyl or phenyl, and m and n stand for O or 1. V

2. A composition of matter comprising acetyl cellulose and a neutral phosphoric acid ester of a monoglycol ether of the general formula V 12 OCzHaOR o=r-o (onnmmn';

O(C2H40)nR" wherein R, R and R" represent alkyl, halogenalkyl or phenyl, and m and n stand for O or 1.

8. A composition of matter comprising a cellulose derivative and a neutral phosphoric wherein R and R represent alkyl, halogenoalkyl or phenyl, and m and n. stand for O or 1.

5. A composition of matter comprising a cellulose derivative and a. neutral phosphoric acid ester of a monoglycol ether of the general formula 0 215140 OiHl O=P0CIHAO CHI,

0 (CIHAO) nR wherein R represents alkyl, halogenoalkyl or phenyl and wherein m means 0 or 1.

6. A. composition of matter comprising acetyl cellulose and a neutral phosphoric acid ester of a monoglycol ether of the general formula OC:H4OC4HI O=P--OC2H4OCH;

O(CxH40)mR wherein R represents alkyl, halogenoalkyl or phenyl and wherein m means 0 or 1.

7. A composition of matter comprising a cellulose derivative and the ester of the formula OCzH4OC4H O=P'OC2H4OCH:

8. A composition of matter comprising acetyl cellulose and the phosphoric acid ester of the formula O=PO CzHaOOHa CURT SCHONBURG.

phosphoric acid 

